Solid substrate coated with silicone resin coating composition

ABSTRACT

A silicone resin coating composition which, when applied to a solid substrate, provides a thick abrasion resistant coating thereto, is disclosed herein. The coating composition has a basic pH in the range of from 7.1-7.8 and is prepared by hydrolyzing an alkyltrialkoxysilane or aryltrialkoxysilane in an aqueous colloidal silica dispersion. A thickening agent is added to the resultant hydrolysis product.

CROSS-REFERENCE TO RELATED APPLICATION

This is a division, of application Ser. No. 082,163 filed Oct. 5, 1979,now U.S. Pat. No. 4,309,319 which in turn is a continuation in part ofapplication Ser. No. 964,910, filed Nov. 30, 1978.

BACKGROUND OF THE INVENTION

This invention relates to a protective coating composition. Moreparticularly, it relates to a silicone resin coating composition which,when applied to a substrate, forms a protective, abrasion-resistantcoating thereon.

Recently, the substitution of glass glazing with transparent materialswhich do not shatter or are more resistant to shattering than glass, hasbecome widespread. For example, transparent glazing made from syntheticorganic polymers is now utilized in public transportation vehicles, suchas trains, buses, taxis and airplanes. Lenses, such as for eye glassesand other optical instruments, as well as glazing for large buildings,also employ shatter-resistant transparent plastics. The lighter weightof these plastics in comparison to glass is a further advantage,especially in the transportation industry where the weight of thevehicle is a major factor in its fuel economy.

While transparent plastics provide the major advantage of being moreresistant to shattering and lighter than glass, a serious drawback liesin the ease with which these plastics mar and scratch, due to everydaycontact with abrasives, such as dust, cleaning equipment and/or ordinaryweathering. Continuous scratching and marring results in impairedvisibility and poor aesthetics, and oftentimes requires replacement ofthe glazing or lens or the like.

One of the most promising and widely used transparent plastics forglazing is polycarbonate, such as that known as Lexan®, sold by GeneralElectric Company. It is a tough material, having high impact strength,high heat deflection temperature, good dimensional stability, as well asbeing self-extinghishing. and is easily fabricated. Acrylics, such aspolymethylmethacrylate, are also widely used transparent plastics forglazing.

Attempts have been made to improve the abrasion resistance oftransparent plastics. For example, scratch-resistant coatings formedfrom mixtures of silica, such as colloidal silica or silica gel, andhydrolyzable silanes in a hydrolysis medium, such as alcohol and water,are known. U.S. Pat. Nos. 3,708,225, 3,986,997 and 3,976,497, forexample, describe such compositions.

In copending U.S. application Ser. No. 964,910 coating compositionshaving improved resistance to moisture and humidity and ultravioletlight are disclosed. It was discovered therein that, in direct contrastto the teachings of U.S. Pat. No. 3,986,997, compositions having a basicpH, i.e., 7.1-7.8, do not immediately gel but in fact provide excellentexcellent abrasion resistant coatings on solid substrates.

In recent months, it has become desirable to even further improve theabrasion resistance offered by the coating compositions of saidcopending U.S. application Ser. No. 964,910.

SUMMARY OF THE INVENTION

Accordingly, it is one object of the present invention to provide anovel protective coating resin for solid substrates.

Another object of this invention is to provide a coating resin for solidsubstrates which, when applied to the substrate, provides an improvedabrasion-resistant surface thereto.

Still another object of the present invention is to provide a coatingresin composition, especially well suited for providing an improvedabrasion resistant surface to transparent substrates without impairingthe optical clarity of the substrate.

A still further object of the present invention is to provide a coatingresin composition which results in an improved abrasion-resistantsurface when applied to metals and metallized surfaces.

These and other objects are accomplished herein by a coating compositioncomprising a dispersion of colloidal silica in an aliphaticalcohol-water solution of the partial condensate of a silanol of theformula RSi(OH)₃, wherein R is selected from the group consisting ofalkyl having from 1 to 3 carbon atoms and aryl, at least 70 weightpercent of the silanol being CH₃ Si(OH)₃, said composition containing 10to 50 weight percent solids, said solids consisting essentially of 10 to70 weight percent colloidal silica and 30 to 90 weight percent of thepartial condensate, said composition further containing a thickeningagent and wherein said composition has a pH of from 7.1 to about 7.8.

DETAILED DESCRIPTION OF THE INVENTION

The coating compositions of this invention are prepared by hydrolyzing atrialkoxysilane or a mixture of trialkoxysilanes of the formulaR'Si(OR)₃, wherein R' is alkyl of from 1 to 3 carbons or aryl, such asphenyl, and R is alkyl in an aqueous dispersion of colloidal silica.

In the practice of the present invention, suitable aqueous colloidalsilica dispersions generally have a particle size of from 5 to 150millimicrons in diameter. These silica dispersions are well known in theart and commercially available ones include, for example, those soldunder the trademarks of Ludox (duPont) and Nalcoag (NALCO Chemical Co.).Such colloidal silicas are available as both acidic and basic hydrosols.For the purpose of this invention, wherein the pH of the coatingcompositions is on the basic side, basic colloidal silica sols arepreferred. However, acidic colloidal silicas, wherein the pH is adjustedto a basic level, are also contemplated. In addition, it has been foundthat colloidal silicas having a low alkali content (e.g., Na₂ O) yield amore stable coating composition. Thus, colloidal silicas having analkali content of less than 0.35% (calculated as Na₂ O) have been foundto be preferable. Moreover, colloidal silicas having average particlesize of from 10 to 30 millimicrons are also preferred. A particularlypreferred aqueous colloidal silica dispersion for the purposes herein isknown as Ludox LS, sold by duPont Company.

In accordance with this invention, the aqueous colloidal silicadispersion is added to a solution of a small amount ofalkyltriacetoxylsilane in alkyltrialkoxysilane or aryltrialkoxysilane.For the purposes herein, from about 0.07 parts by weight, to about 0.1parts by weight, based on 100 parts by weight of the total compositionof the alkyltriacetoxysilane is used. The temperature of the reactionmixture is maintained at about 20° C. to about 40° C., preferably 20° C.to about 30° C., and most preferably below 25° C. It has been found thatin about six to eight hours sufficient trialkoxysilane has hydrolyzed soas to reduce the initial two phase liquid mixture to one liquid phase inwhich the now treated silica (i.e., treated by its admixture with thealkyltrialkoxysilane or aryltrialkoxysilane) is dispersed. In general,the hydrolysis reaction is allowed to continue for a total of about 12to 48 hours, depending upon the desired viscosity of the final product.The more time the hydrolysis reaction is permitted to continue, thehigher will be the viscosity of the product. After the hydrolysis hasbeen completed to the desired extent, the solids content is adjusted bythe addition of alcohol, preferably isoproponal, to the reactionmixture. The use of isopropanol herein has been found to provide betteroptical clarity than if other alcohols, like isobutanol, are used. If,however, excellent optical clarity is not a prime concern, otheralcohols which are suitable dilution solvents include lower aliphaticalcohols, such as methanol, ethanol, propanol, n-butyl alcohol andt-butyl alcohol. Mixtures of such alcohols can be used, too. The solventsystem should contain from about 20 to 75 weight percent alcohol toensure solubility of the partial condensate (siloxanol). Optionally,additional water-miscible polar solvents, such as acetone, butylcellosolve and the like in minor amounts, like no more than 20 weightpercent of the co-solvent system can also be used. The solids content ofthe coating composition of this invention is generally preferred to bein the range of from about 10 to 25%, most preferably, about 13 to about20% by weight of the total composition.

In order to provide the improved abrasion resistance desired herein, athickening agent is added to the resin composition. The thickening agentmay be added either during hydrolysis or after dilution with alcohol asdescribed hereinabove. The addition of the thickening agent results in ahigher viscosity fluid resin which permits a thicker wet film to bedeposited on the substrate which in turn results in a thicker cured filmhaving increased abrasion resistance. Surprisingly, increasing theviscosity of the coating resins herein by the addition of a thickeningagent does not result in a shortened shelf life of the composition aswas found to occur when the viscosity was increased by simply raisingthe solids content of the composition.

Thickening agents suitable for the purposes herein include hydroxypropylguar gum and hydroxypropyl cellulose. Amounts contemplated are about 0.1to about 1%, preferably about 0.1 to about 0.5% by weight of the totalcomposition.

The pH of the resultant coating compositions of the invention is in therange of from about 7.1 to about 7.8, preferably higher than 7.2, suchas from 7.3 to about 7.5. If necessary, dilute base, such as ammoniumhydroxide, or weak acid, such as acetic acid, can be added to thecomposition to adjust the final pH to this desired range. At these basicpH's, the compositions are translucent liquids which are stable at roomtemperature for at least several weeks. When stored at temperaturesbelow about 5° C. (40° F.) the period of stability is increased evenfurther.

The alkyltriacetoxysilane is used to buffer the basicity of the initialtwo liquid phase reaction mixtures and thereby also temper thehydrolysis rate. While the use of alkyltriacetoxysilane is preferredherein, glacial acetic acid may be used in its place, as well as otheracids such as organic acids like propionic, butyric, citric, benzoic,formic, oxalic and the like. Alkyltriacetoxysilanes wherein the alkylgroup contains from 1 to 6 carbon atoms can be used, alkyl groups havingfrom 1 to 3 carbon atoms being preferred. Methyltriacetoxysilane is mostpreferred for the purposes herein.

The silanetriols, RSi(OH)₃, hereinbefore mentioned, are formed in situas a result of the admixture of the corresponding trialkoxysilanes withthe aqueous medium, i.e., the aqueous dispersion of colloidal silica.Exemplary trialkoxysilanes are those containing methoxy, ethoxy,isopropoxy and n-butoxy substituents which, upon hydrolysis, generatethe silanetriol and further liberate the corresponding alcohol. In thisway, at least, a portion of the alcohol content present in the finalcoating composition is provided. Of course, if a mixture oftrialkoxysilanes is employed, as provided for hereinabove, a mixture ofdifferent silanetriols, as well as different alcohols, is generated.Upon the generation of the silanetriol or mixtures of silanetriols inthe basic aqueous medium, condensation of the hydroxyl substituents toform ##STR1## bonding occurs. This condensation takes place over aperiod of time and is not an exhaustive condensation but rather thesiloxane retains an appreciable quantity of silicon-bonded hydroxylgroups which render the polymer soluble in the alcohol-water cosolvent.This soluble partial condensate can be characterized as a siloxanolpolymer having at least one silicon-bonded hydroxyl group per everythree ##STR2## units.

The non-volatile solids portion of the coating composition herein is amixture of colloidal silica and the partial condensate (or siloxanol) ofa silanol. The major portion or all of the partial condensate orsiloxanol is obtained from the condensation of CH₃ Si(OH)₃ and,depending upon the input of ingredients to the hydrolysis reaction,minor portions of partial condensate can be obtained, for example, fromthe condensation of CH₃ Si(OH)₃ with C₂ H₅ Si(OH)₃ or C₃ H₇ Si(OH)₃ ;CH₃ Si(OH)₃ with C₆ H₅ Si(OH)₃, or even mixtures of the foregoing. Foroptimum results in the cured coating it is preferred to use allmethyltrimethoxysilane (thus generating all monomethylsilanetriol) inpreparing the coating compositions herein. In the preferred coatingcompositions herein the partial condensate is present in an amount offrom about 55 to 75 weight percent of the total solids in a cosolvent ofalcohol and water, the alcohol comprising from about 50% to 95% byweight of the cosolvent.

At low solids content, such as about 13%, it has been found that thepolysiloxane polyether copolymers disclosed in copending applicationSer. No. 964,911, filed Nov. 30, 1978, incorporated herein by reference,may be employed in the thickened compositions of this invention as flowcontrol additives which assist in the prevention of flowmarks, dirtmarksand the like on the surface of the substrate which is coated. Generally,these polysiloxane polyether copolymers may be employed in amounts offrom about 2.5 to about 15% by weight of the total solids of thecomposition.

The coating compositions of this invention will cure on a substrate attemperatures of, for example, 120° C. without the aid of an added curingcatalyst. However, in order to employ more desirable milder curingconditions, buffered latent condensation catalysts can be added.Included in this class of catalysts are alkali metal salts of carboxylicacids, such as sodium acetate, potassium formate and the like. Aminecarboxylates, such as dimethylamine acetate, ethanolamine acetate,dimethylaniline formate and the like, quaternary ammonium carboxylatessuch as tetramethylammonium acetate, benzyltrimethylammonium acetate,metal carboxylates, like tin octoate and amines such as triethylamine,triethanolamine, pyridine and the like are also contemplated curingcatalysts herein. Alkali hydroxides, like sodium hydroxide and ammoniumhydroxide can also be used as curing catalysts herein. Moreover, typicalcommercially available colloidal silica, especially those having a basicpH, contain free alkali metal base and alkali metal carboxylatecatalysts will be generated in situ during the hyrolysis reactionherein.

The amount of curing catalyst can be varied within a wide range,depending upon the desired curing conditions. However, in general,catalyst in the amounts of from about 0.05 to about 0.5 weight percent,preferably about 0.1 weight percent, of the composition can be used.Compositions containing catalysts in these amounts can be cured on asolid substrate in a relatively short time at temperatures in the rangeof from about 75°-150° C. to provide a transparent abrasion resistantsurface coating.

The coating compositions of the present invention can be applied to avariety of solid substrates by conventional methods, such as flowing,spraying or dipping, to form a continuous surface film. Optimum coatingthicknesses are obtained by slow dip coating procedures. Substrateswhich are especially contemplated herein are transparent, as well asnon-transparent, plastics and metals. More Particularly, these plasticsare synthetic organic polymeric substrates such as acrylic polymers likepoly(methylmethacrylate), polyesters, such as poly(ethyleneterephthalate), poly(butylene terephthalate), etc., polyamides,polyimides, acrylonitrile-styrene copolymers,styrene-acrylonitrilebutadiene copolymers, polyvinyl chloride,butyrates, polyethylene and the like. The coating compositions of thisinvention are especially useful as coatings for polycarbonates, such asthose polycarbonates known as Lexan®, sold by General Electric Companyand as coatings for injection molded or extruded acrylics, such aspolymethylmethacrylates. Metal substrates on which the presentprotective coatings are also effective include bright and dull metalslike aluminum and bright metallized surfaces like sputtered chromiumalloy. Other solid substrates contemplated herein include wood, paintedsurfaces, leather, glass, ceramics and textiles.

By choice of the proper formulation, application conditions andpretreatment, including the use of primers, of the substrate, thecoatings can be adhered to substantially all solid substrates. A hardcoating having all of the aforementioned characteristics and advantagesis obtained by the removal of the solvent and volatile materials. Thecoating composition will air-dry to a tack-free condition, but heatingin the range of 75° C. to 200° C. is necessary to obtain condensation ofresidual silanols in the partial condensate. This final cure results inthe formation of silsesquioxane (RSiO_(3/2)). In the finished curedcoating the ratio of RSiO_(3/2) units to SiO₂ will range from about 0.43to about 9.0, preferably 1 to 3. A cured coating having a ratio ofRSiO_(3/2) to SiO₂, where R is methyl, of 2 is most preferred. Coatingthicknesses may vary but for the improved abrasion resistance desiredherein, coating thicknesses of 3-10 microns, preferably 5 microns, areutilized.

In order that those skilled in the art may better understand how topractice the present invention, the following examples are given by wayof illustration and not by way of limitation.

EXAMPLES 1-5

80.1 lbs. of Ludox LS (aqueous colloidal silica dispersion, averageparticle size of 12 millimicrons, pH 8.2 sold by duPont) is added, overa period of one-half hour, to a solution of 135 g ofmethyltriacetoxysilane in 97.6 lbs. of methyltrimethoxysilane. Thetemperature of the reaction mixture is maintained between 20° C. and 30°C. The hydrolysis is allowed to proceed over a period of sixteen hours.At this time the reaction mixture is diluted with 182 lbs. ofisopropanol.

Aliquots of 500 g. are taken from the resultant diluted reaction mixtureresin and to each is added 1.5 g of a thickener. The thickeners arehydroxypropyl cellulose (Klucel, Types G, H, and J, sold by HerculesInc.) and hydroxypropyl guar gum. The thickners are added in smallportions to the well-agitated resin samples. The viscosities of theresins are determined using a calibrated Cannon-Fenske routine typeviscometer. The pH of all resins is determined using a Corning Model 10pH meter fitted with a combination pH electrode. The viscosities andpH's are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Example Thickener         Viscosity   pH                                      ______________________________________                                        1(control)                                                                             --                5.3 Centistokes                                                                          7.4                                     2       Klucel, Type G    14.8 Centistokes                                                                          7.35                                    3       Klucel, Type H    74.2 Centistokes                                                                          7.5                                     4       Klucel, Type J     8.8 Centistokes                                                                          7.5                                     5       Hydroxypropyl guar gum                                                                          20.2 Centistokes                                                                          7.4                                     ______________________________________                                    

Plaques of Acrylite FF (extruded transparent acrylic sheet manufacturedby Cyro Industries) are dip coated in these five resins at four inchesper minute. A sixth acrylic plaque is dip coated in the resin of Example3 at two inches per minute. All the plaques are allowed to air dry forone-half hour and are then cured at 85° C. for three hours. Thethickness of the cured films is measured by masking the coated plaquewith pressure sensitive adhesive tape that is resistant to hydrofluoricacid and the coating is etched away in an unmasked area usinghydrofluoric acid. The plaque is rinsed with water. The masking tape isremoved and the thickness of the film is measured using a Talysurfsurface profile measuring device. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Acrylite FF                                                                   Example     4"/Min.     2"/Min.                                               ______________________________________                                        1(control)   60 × 10.sup.-6 in.                                                                 --                                                    2            90 × 10.sup.-6 in.                                                                 --                                                    3           260 × 10.sup.-6 in.                                                                 210 × 10.sup.-6 in.                             4            60 × 10.sup.-6 in.                                                                 --                                                    5           120 × 10.sup.-6 in.                                                                 --                                                    ______________________________________                                    

EXAMPLE 6

Pieces of transparent Lexan® (poly(bisphenol-A carbonate) are primedwith a thermosetting acrylic emulsion (Rhoplex AC 658, sold by Rohm &Haas, a copolymer of n-butylmethacrylate and methylmethacrylate havinghydroxy functionality crosslinked with a substituted melamine, dilutedto 4% solids by using a mixture of 875 parts by weight distilled water,470 parts by weight 2-butoxyethanol and 125 parts by weight Rhoplex AC658 ) allowed to air dry and cured for one-half hour at 120° C. They aredip coated in the composition of Example 3 at two and four inches perminute, allowed to dry for one-half hour and cured one hour at 120° C.The cured coating thicknesses are measured in the same fashion asdescribed above. The results appear in Table 3.

                  TABLE 3                                                         ______________________________________                                        Primed Lexan® Sheet                                                       Coated with the composition of Example 3                                      4"/Min.        2"/Min.                                                        ______________________________________                                        280 × 10.sup.-6 in.                                                                    240 × 10.sup.-6 in.                                      ______________________________________                                    

Other primers may be used such as Rhoplex 1230, also a thermosettingacrylic emulsion sold by Rohm & Haas, or an ethanol-isobutanol solutioncontaining 1.5 weight percent of gamma-aminopropyltriethoxysilane and1.5 weight percent of a preformed reaction product ofgamma-aminopropyltriethoxysilane and maleic anhydride.

EXAMPLE 7

Pieces of Acrylite FF are dip coated in the resin compositions ofExamples 1, 2 and 3 above at a withdrawal rate of four inches perminute. They are allowed to dry and then cured 2 hours at 90° C. Theseplaques are abraded on a falling sand abraser using 250 ml. of 20-30mesh silica sand. Percent haze is measured using a Gardner Hazemeter.The change in percent haze after abrasion is shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Acrylite FF coated with the                                                   composition of Example                                                                            Δ % Haze                                            ______________________________________                                        1                   17.2                                                      2                   10.5                                                      3                   5.5                                                       ______________________________________                                    

An uncoated sheet of Acrylite FF abraded in the same way has a Δ% Hazeof 39.0.

Obviously, other modifications and variations of the present inventionare possible in the light of the above teachings. For example, additivesand other modifying agents, such as pigments, dyes and the like, may beadded to the compositions of this invention. It is to be understood,however, that changes may be made in the particular embodimentsdescribed above which are within the full intended scope of theinvention as defined in the appended claims.

I claim:
 1. A solid substrate having at least one surface coated with animproved aqueous coating composition comprising a dispersion ofcolloidal silica having a particle size of from 5 to 150 millimicrons indiameter in a lower-aliphatic alcohol-water solution of the partialcondensate of a silanol of the formula RSi(OH)₃, wherein thelower-aliphatic alcohol-water solvent contains from about 20 to 75weight percent of said lower-aliphatic alcohol component and wherein Ris selected from the group consisting of alkyl having from 1 to 3 carbonatoms and aryl, at least 70 weight percent of the silanol being CH₃Si(OH)₃, said composition containing 10 to 50 weight percent solidsconsisting essentially of 10 to 70 weight percent colloidal silica and30 to 90 weight percent of the partial condensate, the compositionfurther containing from about 0.1 to about 1 percent by weight of athickening agent selected from the group consisting of hydroxypropylguar gum and hydroxypropyl cellulose, said composition having a pH of7.1 to about 7.8.
 2. An article as defined in claim 1 wherein the solidsubstrate is comprised of a synthetic organic polymer.
 3. An article asdefined in claim 2 wherein said polymer is a transparent polymer.
 4. Anarticle as defined in claim 3 wherein said polymer is a polycarbonate.5. An article as defined in claim 4 wherein said polycarbonate istransparent.
 6. An article as defined in claim 4 wherein saidpolycarbonate is a poly(bisphenol-A carbonate).
 7. An article as definedin claim 2 wherein said polymer is a polymethylmethacrylate.
 8. Anarticle as defined in claim 7 wherein said polymethylmethacrylate istransparent.
 9. An article as defined in claim 1 wherein the aqueouscoating composition has been cured on said surface of said solidsubstrate.
 10. An article as defined in claim 1 wherein said surface ofsaid solid substrate has been primed with a primer composition prior tohaving been coated with said aqueous coating composition.
 11. An articleas defined in claim 10 wherein said primer composition is comprised of athermosetting acrylic emulsion.
 12. An article as defined in claim 10wherein said primer composition is comprised of an ethanol-isobutanolsolution containing 1.5 weight percent ofgamma-aminopropyltriethoxysilane and 1.5 weight percent of a preformedreaction product of gamma-aminopropyltriethoxysilane and maleicanhydride.